EP3662996A2 - Molybdän- oder wolframkomplexe als olefinmetathesekatalysatoren und reaktionen unter verwendung dieser katalysatoren - Google Patents

Molybdän- oder wolframkomplexe als olefinmetathesekatalysatoren und reaktionen unter verwendung dieser katalysatoren Download PDF

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EP3662996A2
EP3662996A2 EP19210969.2A EP19210969A EP3662996A2 EP 3662996 A2 EP3662996 A2 EP 3662996A2 EP 19210969 A EP19210969 A EP 19210969A EP 3662996 A2 EP3662996 A2 EP 3662996A2
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Prior art keywords
optionally substituted
phenyl
alkyl
olefin
compound
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EP19210969.2A
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English (en)
French (fr)
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EP3662996A3 (de
Inventor
Levente Ondi
Jeno VARGA
Ágota BUCSAI
Florian Toth
Krisztian LORINCZ
Csaba Hegedus
Emmanuel Robe
Georg Emil FRÁTER
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Verbio Vereinigte Bioenergie AG
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Verbio Vereinigte Bioenergie AG
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Definitions

  • This invention relates to alkene metathesis reactions and metathesis catalysts suitable for use in said reactions.
  • Alkene metathesis is a reaction between alkenes or olefinic groups, in which formally alkylidene groups are exchanged between the alkenes or olefinic groups.
  • Examples of metathesis reactions include cross metathesis, i.e.
  • the latter reaction may be regarded as a cross metathesis between two identical olefins. More generally, any two identical olefins may be reacted in a homo cross metathesis reaction.
  • US 2011/007742 A1 relates generally to catalysts and processes for the Z-selective formation of internal olefin(s) from terminal olefin(s) via homo-metathesis reactions.
  • the method comprises reacting a first molecule comprising a terminal double bond and a second, identical molecule via a homo-metathesis reaction to produce a product comprising an internal double bond, wherein the internal double bond of the product comprises one carbon atom from the terminal double bond of the first molecule and one carbon atom from the terminal double bond of the second carbon atom, and wherein at least about 60 % of the internal double bond of the product is formed as the Z-isomer.
  • This reaction is catalyzed by a compound of formula wherein M is Mo or W, R 1 is aryl, heteroaryl, alkyl, heteroalkyl, optionally substituted, R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl, optionally substituted, and R 4 and R 5 can be the same or different and are alkyl, heteroalkyl, aryl, heteroaryl, silylalkyl, or silyloxy, optionally substituted, wherein at least one of R 4 or R 5 is a ligand containing oxygen bound to M.
  • bidentate structures may be used as ligand R 4 .
  • Such catalysts usually are applied or have to be applied in a metathesis reaction in a relatively high molar amount with respect to the molar amount of olefin or olefins in order to achieve a sufficient degree of conversion of the olefin(s) used as starting material. It is known that a molar ratio up to 1 : 500 with respect to the applied olefin(s) (molar ratio catalyst : olefin(s)) is necessary in order to achieve a conversion of 30 % or more. Accordingly, and since these catalysts are relatively costive, such reactions are costive at an industrial scale, and thus often lack industrial applicability.
  • the process and the compounds should be able to allow for a conversion in a metathesis reaction of at least 30 % when applied in a molar ratio of less than 1 : 500 with respect to the olefin(s) to be reacted.
  • Such conversion and molar ratio are considered to allow for a beneficial reaction at an industrial scale.
  • this object is achieved with a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i):
  • R 1 to R 5 are selected such that a conversion of at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 % or at least 90 % is achieved.
  • R 1 to R 5 are selected such that the molar ratio of the compound of the above formula to first or the second olefin is 1 : 1,000 or less, or 1 : 2,500 or less, or 1 : 5,000 or less, or 1 : 7,500 or less, or 1 : 10,000 or less in order to achieve the object of the invention.
  • R 1 to R 5 are selected such that the molar ratio is less than 1 : 500, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • R 1 to R 5 are selected such that the molar ratio is 1 : 1,000 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • R 1 to R 5 are selected such that the molar ratio is 1 : 2,500 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • R 1 to R 5 are selected such that the molar ratio is 1 : 5,000 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • R 1 to R 5 are selected such that the molar ratio is 1 : 7,500 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • R 1 to R 5 are selected such that the molar ratio is 1 : 10,000 or less, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • R 1 to R 5 are selected such that the molar ratio is 1 : 20,000 or less, or 1 : 50,000 or less, or 1 : 100,000 or less, or 1 : 500,000 or less, or 1 : 1,000,000 or less, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %, respectively.
  • the upper limit of the molar ratio of said compound, which catalyzes said metathesis reaction, to the first or second olefin is 1 : 2,000,000.
  • R 1 to R 5 are selected such that the molar ratio is from less than 1 : 500 to 1 : 50,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • R 1 to R 5 are selected such that the molar ratio is from 1 : 1,000 to 1 : 40,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • R 1 to R 5 are selected such that the molar ratio is from 1 : 2,500 to 1 : 30,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • R 1 to R 5 are selected such that the molar ratio is from 1 : 5,000 to 1 : 30,000 or less, or from 1 : 10,000 to 1 : 30,000, or from 1 : 15,000 to 1 : 30,000, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %, respectively.
  • the method consists of step (i).
  • the first olefin has a terminal olefinic double bond
  • the second olefin has a terminal olefinic double bond
  • this reaction may be denoted as a homo-metathesis reaction.
  • This reaction results in an olefin having an internal olefinic double bond, which is made from an olefin having a terminal olefinic double bond.
  • Such reaction may also be termed as a cross-metathesis reaction between two identical olefins (homo-cross metathesis reaction).
  • the invention relates to a method of forming an olefin having an internal olefinic double bond from an olefin having a terminal olefinic double bond in a metathesis reaction, comprising step (i.1):
  • step (i.1) may be performed according to methods and conditions known from the prior art, e.g. known from US 2011/0077421 .
  • At least 50 % of the internal double bond is formed as the Z-isomer, further preferred more than 60 %, still more preferred more than 70 %, or more than 80 %, or more than 90 %.
  • first and the second olefin are different from one another.
  • Such reaction may be termed as a cross-metathesis reaction between two different olefins.
  • the invention relates to a method of forming an olefin (or olefins) from a first olefin and a second olefin in a metathesis reaction, comprising step (i.2):
  • the first and the second olefin have an internal olefinic double bond, respectively.
  • first and the second olefin have a terminal olefinic double bond, respectively.
  • the first olefin has a terminal olefinic double bond
  • the second olefin has an internal olefinic group, or vice versa.
  • the first olefin is an olefin having an internal olefinic double bond and the second olefin is ethylene.
  • Such metathesis reaction may be termed as ethenolysis. This ethenolysis reaction results in an olefin or olefins having a terminal olefinic double bond, respectively.
  • the invention relates to a method of forming an olefin having a terminal olefinic double bond from a first olefin having an internal olefinic double bond and a second olefin, wherein the second olefin is ethylene, comprising step (i.3):
  • the first olefin is a cyclic olefin and the second olefin is a cyclic olefin, wherein the metathesis reaction is a ring opening polymerization metathesis.
  • the invention relates to a method of forming a polymer comprising internal olefinic double bonds from a first cyclic olefin and a second cyclic olefin in a ring opening polymerization metathesis, comprising step (i.4):
  • the first olefin is identical to the second olefin.
  • the olefin is selected from norbornene or cyclopentadiene.
  • the method consists of step (i.1) or step (i.2) or step (i.3) or step (i.4).
  • the invention relates to a method of forming an olefin from a first olefin and a second olefin in a metathesis reaction, comprising step (i):
  • M Mo or W;
  • R 1 is aryl, or adamant-1-yl; optionally substituted;
  • R 2 is an alkyl or cycloalkyl moiety which is bound to M via a tertiary carbon atom such as -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is alkoxy, heteroaryl, silyloxy; aryloxy; optionally substituted;
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from triphenylsilyloxy or triisopropylsilyloxy
  • M Mo or W;
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from 9-phenyl-fluorene-9-yloxy;
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2,6-diphenylphenoxy; 9-phenyl-fluorene-9-yloxy; t-butyloxy; and R 4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenyl
  • residues R 4 and R 5 are linked and are bound to M via oxygen, respectively.
  • An example of such a linked residue is the corresponding residue in compounds 105 and 114:
  • the catalysts may be prepared according to known methods or methods e.g. known from US 2011/0077421 A1 , US 6,121,473 , US 2008/0119678 and US 2011/0015430 .
  • the compounds may be advantageously used in metathesis reactions specified above. Without being bound by theory, it is believed that in particular R 4 as selected and defined provides for a high yield and stereoselectivity in the various types of metathesis reactions.
  • the starting materials of the catalysts in particular the starting materials used to introduce residue R 4 into the Mo or W-compound are mostly commercially available or may be simply prepared according to known methods. This makes the selected catalysts particularly applicable for industrial purposes, i.e. for alkene metathesis reactions performed at an industrial scale.
  • said catalysts may advantageously be applied in various types of metathesis reactions.
  • the first olefin has a terminal olefinic double bond
  • the second olefin has a terminal olefinic double bond, wherein the first and the second olefin are identical.
  • first and the second olefin are different from one another.
  • the first olefin has an internal olefinic double bond and the second olefin is ethylene.
  • R 1 is 2,6-diisopropylphenyl; R 2 is -C(CH 3 ) 2 C 6 H 5 ; R 3 is H; R 4 is 1-(4-bromo-2,6-diphenylphenoxy); R 5 is 2,5-dimethyl-pyrrol-1-yl; or when M is Mo; R 1 is 2,6-dimethylphenyl; R 2 is -C(CH 3 ) 2 C 6 H 5 ; R 3 is H; R 4 is 4-bromo-2,3,5,6-tetraphenylphenoxy; R 5 is 2,5-dimethyl-pyrrol-1-yl; the catalysts allow for ethenolysis resulting in a high yield of an olefin having a terminal olefinic double bond.
  • Further preferred compounds used as catalysts in the method according to the invention are the following compounds 1 to 291: 180 181 182 C47H51FMoN202 C59H58BrFMoN202 C55H71Br2FMoN203Si 790.87 1021.96 1111.01 10.9 11.73 12.99, 13.55 183 184 185 C43H50BrFMoN20 C32H34BrCl2FN20W C25H30Cl2N2O 3 W 805.71 814.07 661.23 11.62 8.43 9.17 186 187 188 C26H27Cl2N30W C46H49ClMoN2O C35H33Cl3N2OW 652.26 777.29 787.25 10.34 11.7 8.04 189 190 191 C47H41BrCl2MoN2O C52H43BrCl2N2OW C52H44Cl2N2OW 896,6 1046,56 967,66 10.73 7.98 01.aug 192
  • the molar ratio of metathesis catalyst and first or second olefin or first and second olefin can be further decreased if the feedstock comprising said first and/or said second olefin that are to be subjected to said metathesis reaction is purified prior to its reaction at the catalyst.
  • purification is performed such that by-products (contaminants) being contained in said feedstock are subjected to a physical purification.
  • physical purification encompasses: distilling said by-products off, or distilling the feedstock, or adsorbing said by-products. Accordingly, said by-products may be partially or completely removed from the feedstock such that they do not negatively affect the catalyst to be employed.
  • Possible by-products accompanying said first and said second olefin, which are comprised in said feedstock are e.g. water, alcohols, aldehydes, peroxides, hydroperoxides, protic materials, polar materials, Lewis base (basic) catalyst poisons and two or more thereof.
  • the by-products are selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, and two or more thereof.
  • purification is a chemical purification.
  • chemical purification encompasses: subjecting the by-products to a chemical reaction.
  • the by-product(s) may be converted to another compound, which does not negatively affect the catalyst to be employed.
  • physical purification comprises means selected from the group consisting of heat (preferably distillation), molecular sieves, alumina, silica gel, montmorillonite clay, Fuller's earth, bleaching clay, diatomaceous earth, zeolites, kaolin, activated metals, metal sulfates, metal halides, metal silicates, activated carbon, and soda ash.
  • chemical purification comprises means selected from the group consisting of metal carbonates and metal hydrogen carbonates, acid anhydrides, metal hydrides, phosphorous pentoxide, metal aluminum hydrides, alkyl aluminum hydrides, trialkyl aluminums, metal borohydrides, organometallic reagents, metal amides, and combinations thereof.
  • a by-product is a compound that contains at least one proton that is suitable to react with a compound selected from the group consisting of metal carbonates and metal hydrogen carbonates, acid anhydrides, metal hydrides, phosphorous pentoxide, metal aluminum hydrides, alkyl aluminum hydrides, trialkyl aluminums, metal borohydrides, organometallic reagents, metal amides, and combinations thereof.
  • purification is performed by means selected from the group consisting of optionally heat-treated molecular sieves, optionally heat-treated activated alumina, optionally heat-treated activated acidic alumina, optionally heat-treated activated neutral alumina, optionally heat-treated activated basic alumina, alkaline earth metal hydrides, alkaline earth metal sulfates, alkali metal sulfates, alkali earth metal halides, alkali metal aluminum hydrides, alkali metal borohydrides, Grignard reagents; organolithium reagents, trialkyl aluminums, metal bis(trimethylsilyl)amides, and combinations thereof.
  • optionally heat-treated molecular sieves optionally heat-treated activated alumina, optionally heat-treated activated acidic alumina, optionally heat-treated activated neutral alumina, optionally heat-treated activated basic alumina, alkaline earth metal hydrides, alkaline earth metal sulfates, alkali metal
  • purification is performed by means selected from the group consisting of CaH 2 , activated Cu, activated Mg, acetic anhydride, calcium sulfate, magnesium sulfate, potassium sulfate, aluminum sulfate, potassium magnesium sulfate, sodium sulfate, calcium carbonate, sodium carbonate, magnesium silicate, potassium chloride, LiAlH 4 , NaAlH 4 , iBu 2 AlH, n-butyl lithium, t -butyl lithium, sec-butyl lithium, triethyl aluminum, tributyl aluminum, triisopropyl aluminum, trioctyl aluminum, lithium diisopropyl amide, KHMDS, and combinations thereof.
  • said first and said second olefin are comprised in a feedstock
  • said feedstock further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, or a mixture of two or more thereof
  • the method further comprises step (0) prior to step (i): (0) subjecting said feedstock to a physical or chemical or physical and chemical purification step, preferably wherein said physical purification is performed prior to the chemical purification step, wherein the physical purification step comprises: distilling at least one of said by-products off, or distilling said feedstock, or adsorbing at least one of said by-products; and wherein the chemical purification step comprises: subjecting at least one of said by-products to a chemical reaction.
  • said first and said second olefin are comprised in a feedstock, wherein said feedstock further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides and hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, or a mixture of two or more thereof, the method further comprising step (0) prior to step (i) (0) subjecting at least one of the by-products in said feedstock to a chemical reaction.
  • the first and the second olefin are identical.
  • the feedstock comprises at least 99 % by weight of the first and the second olefin based on the total weight of the feedstock, the remainder being by-products, or at least 99.5 % by weight.
  • the feedstock comprises at least 99.9 % by weight of the first and the second olefin, or at least 99.99 % by weight, or at least 99.999 %.
  • step (0) transfers by-products being contained in the olefin and which may react with a metathesis catalyst and thus may destroy activity thereof, into non-reactive species, thereby further favorably decreasing the molar ratio of catalyst to olefin.
  • the by-products of the feedstock are subjected to an anhydride of an organic acid.
  • Suitable anhydrides are preferably the anhydrides of aliphatic, cyclic, alicyclic organic acids having from 1 to 10 carbon atoms, or an aromatic organic acid having from 6 to 10 carbon atoms.
  • Such compounds are known in the art or may be produced according to known methods.
  • the organic anhydride is acetic anhydride.
  • the by-products of the feedstock are subjected to an organometallic compound of aluminum.
  • the organometallic compound is of formula R 1 R 2 R 3 Al, wherein R 1 , R 2 , and R 3 are independently selected from an aliphatic, cyclic, alicyclic residue having from 1 to 10 carbon atoms, or from aromatic residues having from 6 to 10 carbon atoms.
  • R 1 , R 2 , and R 3 are independently selected from an aliphatic, cyclic, alicyclic residue having from 1 to 10 carbon atoms, or from aromatic residues having from 6 to 10 carbon atoms.
  • the organometallic compound of aluminum is triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, or trioctyl.
  • Trioctyl aluminum is particularly preferred since said compound is stable in contact with air, i.e. is not-flammable in contact with air, contrary to e.g. triethyl aluminum. This renders said compound particularly suitable for applications at an industrial scale.
  • the amount of by-products may be determined, e.g. by known methods such as chromato-graphical methods. Then, the theoretical amount of compound needed to convert reactive groups of the by-products into non-reactive groups, preferably organic anhydride or organometallic aluminum compound, is added.
  • a slight excess of organic anhydride or organometallic aluminum compound preferably a trialkyl aluminum compound, preferably trioctyl aluminum, is added in order to convert said by-product into a species which is not reactive towards the catalyst.
  • a trialkyl aluminum compound preferably trioctyl aluminum
  • per 1 mole of by-product preferably 1 to 2 mole of trialkyl aluminum compound, preferably trioctyl aluminum, is used, preferably 1 to 1,5 mole, more preferred 1 to 1,25 mole.
  • any excess of organometallic aluminum compound may be destroyed or removed.
  • step (0) and step (i) may be performed spatially separated from each other.
  • step (0) may be performed in one place or in one reaction vessel, and step (i) is performed at another place or in another reaction vessel.
  • step (0) and step (i) are performed spatially not separated from each other.
  • step (0) is performed in one place or in one reaction vessel
  • step (i) is performed in the same place or in the same reaction vessel.
  • the means used to purify said feedstock prior to a metathesis reaction comprises an adsorbent which, in some embodiments, is selected from the group consisting of silica gel, alumina, bleaching clay, activated carbon, molecular sieves, zeolites, Fuller's earth, diatomaceous earth, and the like, and combinations thereof.
  • the means is selected from the group consisting of optionally heat-treated molecular sieves, optionally heat-treated alumina, and a combination thereof.
  • the adsorbent comprises optionally heat-treated activated alumina which, in some embodiments, is selected from the group consisting of optionally heat-treated activated acidic alumina, optionally heat-treated activated neutral alumina, optionally heat-treated activated basic alumina, and combinations thereof.
  • the absorbent comprises optionally heat-treated activated neutral alumina, which can be useful in treating substrates (e.g., olefins) that are susceptible to acid-catalyzed isomerization and/or rearrangement.
  • the means for purification comprises an adsorbent (e.g., molecular sieves, alumina, etc.)
  • an adsorbent e.g., molecular sieves, alumina, etc.
  • the treating of the feedstock with the adsorbent is more effectively performed by flowing the feedstock through the means for purification using a percolation- or flow-type system (e.g., chromatography column) as opposed to simply adding the adsorbent to the substrate in a container.
  • a percolation- or flow-type system e.g., chromatography column
  • about 20 wt% of alumina is used in a column.
  • the means used for purifying the feedstock prior to a metathesis reaction comprises a trialkyl aluminum which, in some embodiments, is selected from the group consisting of triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof. While neither desiring to be bound by any particular theory nor intending to limit in any measure the scope of the appended claims or their equivalents, it is presently believed that the treatment of a substrate with a trialkyl aluminum greatly improves feedstock conversions at low concentrations of metathesis catalyst but that in the presence of excess trialkyl aluminum, catalyst performance is adversely affected.
  • a successive agent used to treat the substrate can comprise an adsorbent which can remove excess trialkyl aluminum.
  • the amount of trialkyl aluminum used for treatment of the feedstock can be reduced by first treating the feedstock with a different means of a type described herein (e.g., an adsorbent including but not limited to molecular sieves, alumina, and/or the like), and then introducing the trialkyl aluminum as a second (or subsequent) means to remove residual contaminants.
  • molecular sieves can be used as a means for bulk drying a feedstock, "high heat-treated" alumina can then be used as a second means to remove additional moisture, and finally molecular sieves can be used at the end as a third means for removing still further residual moisture.
  • molecular sieves can be used as a first means for bulk drying a substrate, "high heat-treated” alumina can then be used as a second means to remove additional moisture, and finally a trialkyl aluminum (e.g., triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof) can be used as a third means for removing any further residual moisture.
  • a trialkyl aluminum e.g., triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof
  • activated copper powder is used alone or in combination with another treatment.
  • activated copper powder is used in combination with heat (e.g., 200 °C for at least 2 hours under nitrogen gas), molecular sieves, and/or a trialkyl aluminum treatment.
  • activated magnesium turnings are used alone or in combination with another treatment.
  • activated magnesium turnings are used in combination with heat (e.g., 200 °C for at least 2 hours under nitrogen gas), molecular sieves, and/or a trialkyl aluminum treatment.
  • acetic anhydride is used alone or in combination with another treatment/means.
  • acetic anhydride is used in combination with alumina (aluminum oxide) and/or a trialkyl aluminum treatment.
  • acetic anhydride is used in combination with alumina, distillation, molecular sieves, and/or a trialkyl aluminum treatment. Further, percolation on activated alumina or molecular sieves can be applied before or instead of the trialkyl aluminum treatment.
  • alumina is used alone or in combination with another treatment/agent. In one embodiment, alumina is used in combination with a palladium on carbon (Pd/C) catalyst and/or a trialkyl aluminum treatment.
  • Pd/C palladium on carbon
  • the purification period of the feedstock may significantly influence efficacy of the chemical purification step. Accordingly, prolonged purification periods may improve catalytic activity of the compounds used as catalysts in the metathesis reactions according to the invention.
  • the feedstock is subjected to said compound for a period of from 2 to 100 h, preferably 5 to 90 h, more preferred 10 to 80 h, and still more preferred 15 to 70 h.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of 1 : 1,000 or less, or 1 : 2,500 or less, or 1 : 5,000 or less, or 1 : 7,500 or less, or 1 : 10,000 or less.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of less than 1 : 500, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of 1 : 1,000 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of 1 : 2,500 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the purification provides a molar ratio of 1 : 5,000 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of 1 : 7,500 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of 1 : 10,000 or less, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of 1 : 20,000 or less, or 1 : 50,000 or less, or 1 : 100,000 or less, or 1 : 500,000 or less, or 1 : 1,000,000 or less, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %, respectively.
  • the purification provides for a lower limit of the compound of the above formula to the first and/or the second olefin of the molar ratio of 1 : 2,000,000, or 1 : 3,000,000 or 1 : 4,000,000, respectively.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of less than 1 : 500 to 1 : 50,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of from 1 : 1,000 to 1 : 40,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of from 1 : 2,500 to 1 : 30,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • the purification of the feedstock reduces the level of the at least one by-product by an amount sufficient to enable the metathesis reaction to proceed at a molar ratio of the compound of the above formula to the first and/or the second olefin of from 1 : 5,000 to 1 : 30,000 or less, or from 1 : 10,000 to 1 : 30,000, or from 1 : 15,000 to 1 : 30,000, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %, respectively.
  • said method consists of steps (0) and (i).
  • the efficacy of the compound of the above formula used as metathesis catalyst may be improved through slow addition of the catalyst to the first and/or second olefin.
  • the efficacy may be e.g. evaluated by calculating the turn-over-number (TON).
  • TON turn-over-number
  • the overall catalyst loading may be decreased by at least 10 %, at least 20 %, or at least 30 % in comparison to achieve the same TON as a single, full batch loading.
  • the slow addition of overall catalyst loading may comprise adding fractional catalyst loadings to the substrate at an average rate of approximately 10 ppmwt catalyst per hour (ppmwt/hr), 5ppmwt/hr, 1 ppmwt/hr, 0.5 ppmwt/hr, 0.1 ppmwt/hr, 0.05 ppmwt/hr, or 0.01 ppmwt/hr.
  • the catalyst is slowly added at a rate of between about 0.01-10 ppmwt/hr, 0.05-5 ppmwt/hr, or 0.1-1 ppmwt/hr.
  • the slow addition of the catalyst may be conducted in batch loadings at frequencies of every 5 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 12 hours, or 1 day. In other embodiments, the slow addition is conducted in a continuous addition process.
  • the catalyst is slowly added to the substrate at a rate of from 0.01-10 ppmwt catalyst per hour.
  • the catalyst is added in portions.
  • the feedstock comprising the first and/or second olefin is purified with at least one means as described in detail above prior to the slow addition of the catalyst.
  • the slow addition of the catalyst improves the efficacy of the catalyst independent of any treatment of the substrate.
  • the feedstock is purified applying prolonged purification periods followed by a slow addition of the catalyst.
  • the invention relates to compounds that may be used in the method as defined in the first aspect of the invention and in any embodiment defined therein.
  • the invention relates to a compound of formula wherein
  • R 6 is phenyl, which bears two substituents in ortho position with respect to O, or which bears two substituents in ortho position with respect to O and a substituent in para position with respect to O, wherein the two substituents in ortho position are identical.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-butyloxy; and R 4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenyl
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • M is Mo or W
  • R 1 is 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-butyloxy; and R 4 is selected from 2,6-diphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2,6-d
  • M is Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • M is Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • the invention relates to a compound of formula
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-methoxy-2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-fluoro-2,6-dimesitylphenoxy, 4-bromo-2,6-di-tert.-butylphenoxy, 4-methoxy-2,6-di-tert.-butylphenoxy, 4-methyl-2,6-di-tert.-butylphenoxy, 2,4,6-tri-tert.-butylphenoxy, 4-bromo-2,3,5,6-tetraphenylphenoxy, 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy.
  • the invention relates to a compound of formula
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 4 is selected from 2,6-diphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2,6-di(tert.-butyl)phenoxy.
  • the invention relates to a compound of formula wherein
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyl; triisopropylsilyl; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; t-butyloxy.
  • the invention relates to a compound of formula
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyl; triisopropylsilyl; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 9-phenyl-fluorene-9-yloxy; t-butyloxy.
  • M Mo or W;
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl;
  • R 4 is R 6 -X-, wherein R 6 -X- is selected from 1-(2,6-di-t-butylphenoxy); wherein the phenyl moiety of the phenoxy residue preferably bears up to three substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl, isopropyl or t-butyl, alkoxy, such as C 1 -C 4 alkoxy, phenoxy, phenyl, halogen.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl
  • R 4 is R 6 -X-, wherein R 6 -X- is selected from 4-methyl-2,6-di-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy or 4-bromo-2,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy.
  • M W;
  • R 1 is 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is pyrrol-1-yl;
  • R 4 is 4-bromo-2,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy.
  • M Mo
  • R 1 is 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 5 is pyrrol-1-yl
  • R 4 is 4-methyl-2,6-di-t-butylphenoxy or 4-bromo-2,6-dit-butylphenoxy or 2,4,6-tri-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy.
  • M Mo or W;
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl;
  • R 4 is R 6 -X-, wherein R 6 -X- is selected from 2,6-di-phenylphenoxy; wherein the phenyl moiety of the phenoxy residue preferably bears up to three substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl, isopropyl or t-butyl, alkoxy, such as C 1 -C 4 alkoxy, halogen, phenoxy, phenyl, optionally substituted, respectively.
  • M Mo or W;
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from pyrrol-1-yl and 2,5-dimethyl-pyrrol-1-yl;
  • R 4 is R 6 -X-, wherein R 6 -X- is selected from 2,6-diphenylphenoxy, 4-chloro-2,6-diphenylphenoxy, 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy, 2,3,5,6-tetraphenylphenoxy or 4-chloro-2,3,5,6-tetraphenylphenoxy or 4-bromo-2,
  • M Mo
  • R 1 is selected from 2,6-diisopropylphenyl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is pyrrol-1-yl
  • R 4 is 2,6-diphenylphenoxy, 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy.
  • M Mo
  • R 1 is selected from 2,6-dimethylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is 2,5-dimethyl-pyrrol-1-yl
  • R 4 is selected from 2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy.
  • M Mo
  • R 1 is selected from adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 5 is 2,5-dimethyl-pyrrol-1-yl
  • R 4 is 2,6-diphenylphenoxy.
  • M Mo
  • R 1 is 2,6-dimethylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is 2,5-dimethyl-pyrrol-1-yl
  • R 4 is selected from 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-di(2,4,6-trimethylphenyl)phenoxy.
  • M Mo
  • R 1 is 2,6-dimethylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl
  • R 4 is 9-phenyl-fluorene-9-yloxy.
  • M is Mo;
  • R 1 is 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl;
  • R 4 is 9-phenyl-fluorene-9-yloxy.
  • M Mo
  • R 1 is 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl
  • R 4 is 2-phenyl-1,1,1,3,3,3-hexafluoroprop-2-yloxy.
  • M Mo
  • R 1 is 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl
  • R 4 is triphenylsilyloxy.
  • M W;
  • R 1 is selected from 2,6-diisopropylphenyl, 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is 2,5-dimethyl-pyrrol-1-yl;
  • R 4 is triphenylsilyloxy.
  • M Mo
  • R 1 is selected from 2,6-diisopropylphenyl; 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is pyrrol-1-yl;
  • R 4 is triphenylmethyloxy.
  • M Mo;
  • R 1 is 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is 2,5-dimethyl-pyrrol-1-yl;
  • R 4 is triphenylmethyloxy.
  • R 1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 4 is 4-bromo-2,6-diphenylphenoxy or 4-bromo-2,3,5,6-tetraphenylphenoxy
  • R 5 is pyrrol-1-yl or 2,5-dimethyl-pyrrol-1-yl.
  • M Mo
  • R 1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 4 is 4-bromo-2,6-diphenylphenoxy
  • R 5 is 2,5-dimethyl-pyrrol-1-yl.
  • M Mo
  • R 1 is 2,6-dimethylphenyl or 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 4 is 4-bromo-2,3,5,6-tetraphenylphenoxy
  • R 5 is 2,5-dimethyl-pyrrol-1-yl.
  • M Mo
  • R 1 is 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 4 is 2,6-di-t-butylphenoxy
  • the phenyl moiety of the phenoxy residue preferably bears up to three substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl or t-butyl, alkoxy, such as C 1 -C 4 alkoxy, phenoxy, phenyl, halogen
  • R 5 is pyrrol-1-yl.
  • M Mo
  • R 1 is 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 4 is 4-methyl-2,6-di-t-butylphenoxy or 4-methoxy-2,6-di-t-butylphenoxy or 4-bromo-2,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy
  • R 5 is pyrrol-1-yl.
  • M W;
  • R 1 is 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is pyrrol-1-yl;
  • R 4 is 4-methoxy-2,6-di-t-butylphenoxy or 4-bromo-2,6-di-t-butylphenoxy or 2,4,6-tri-t-butylphenoxy.
  • Each of these three W-based compounds of the afore-mentioned embodiment when used as a catalyst in a cross metathesis reaction, may provide for excellent Z-selectivity, which may be around 90 % Z and around 10 % E.
  • M Mo
  • R 1 is 2,6-diisopropylphenyl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or - C(CH 3 ) 3
  • R 3 is H
  • R 4 is 4-bromo-2,6-diphenylphenoxy or 4-bromo-2,3,5,6-tetraphenylphenoxy
  • R 5 is pyrrol-1-yl.
  • M Mo; or W;
  • R 1 is selected from 2,6-dimethylphenyl; 2,6-diisopropylphenyl; or 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 4 is 2,6-diphenylphenoxy or 2,6-di-t-butylphenoxy; wherein the phenyl moiety of the phenoxy residue preferably additionally to the two phenyl or t-butyl residues bears up to three substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl or t-butyl, alkoxy, such as C 1 -C 4 alkoxy, phenoxy, phenyl, halogen;
  • R 5 is pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl.
  • M Mo; or W;
  • R 1 is selected from 2,6-dimethylphenyl; 2,6-diisopropylphenyl; or 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 ; -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 4 is 2,6-diphenylphenoxy or 2,6-di-t-butylphenoxy; wherein the phenyl moiety of the phenoxy residue additionally to the two phenyl or t-butyl residues bears up to three substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl or t-butyl, alkoxy, such as C 1 -C 4 alkoxy, halogen, phenoxy, phenyl, optionally substituted, respectively;
  • R 5 is pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl.
  • M is Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or-C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from triphenylsilyloxy
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from 9-phenyl-fluorene-9-yloxy
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-di-t-butylphenyl, 2,6-dichlorophenyl, adamant-1-yl
  • R 2 is - C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from 2-phenyl-1,1,1,3,3,3-hexafluoroprop-2-oxy or 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy
  • M W;
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 2 is -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl;
  • M Mo or W;
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, adamant-1-yl;
  • R 2 is -C(CH 3 ) 3 ;
  • R 3 is H;
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; 9-phenyl-fluorene-9-yloxy; 2-phenyl-1,1,1,3,3,3-hexafluoroprop-2-yloxy;
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl
  • R 2 is -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl
  • R 4 is selected from 2,6-diphenylphenoxy, 4-bromo-2,6-diphenylphenoxy, 4-fluoro-2,6-diphenylphenoxy, 4-methyl-2,6-diphenylphenoxy, 4-dimethylamino-2,6-diphenylphenoxy, 2,6-di(2,4,6-triisopropylphenyl)phenoxy, 4-fluoro-2,6-dimesitylphenoxy, 2,6-di-tert.-butylphenoxy, 4-bromo-2,6-di-tert.-butylphenoxy, 4-methoxy-2,6
  • the invention relates to a compound of structure 2, 3, 4, 5, 6, 7, 8, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 23, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, 52, 53, 54, 55, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 73, 74, 75, 77, 79, 81, 82, 83, 84, 85, 86, 89, 91, 94, 95, 97, 99, 100, 104, 105, 107, 108, 109, 111, 114, 115, 116, 117, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137
  • compounds are preferably selected from the group consisting of structures 11, 32, 36, and 162. Also preferred are compounds selected from the group consisting of structures 30, 123, 142, 154, 168, and 178. Also preferred is the compound of structure 21.
  • the invention relates to the use of a compound as defined in the second aspect or in any embodiment of the second aspect as catalyst, preferably wherein the catalyst catalyzes a metathesis reaction. Accordingly, the compounds may be used in a metathesis reaction or as catalyst in a metathesis reaction.
  • the metathesis reaction is selected from cross metathesis, ring opening metathesis, ring opening polymerization metathesis, ring closing metathesis, ethenolysis, homo-metathesis.
  • Cross metathesis may e.g. be performed as a homo cross metathesis, i.e. the metathesis reaction between identical olefins (HCM) or as a hetereo cross metathesis reaction, i.e. the reaction between two different olefins.
  • HCM olefins
  • hetereo cross metathesis reaction i.e. the reaction between two different olefins.
  • the invention relates to a kit comprising an organometallic compound of aluminum of formula R 1 R 2 R 3 Al, wherein R 1 , R 2 , and R 3 are independently selected from an aliphatic, cyclic, alicyclic residue having from 1 to 10 carbon atoms, or from aromatic residues having from 6 to 10 carbon atoms; and a compound used in the method of the invention, preferably a compound selected from one or more of the structures 1 to 291.
  • the organometallic compound of aluminum used in the kit is triocty aluminum.
  • the invention relates to a kit consisting of said organometallic compound of aluminum of formula R 1 R 2 R 3 Al and said compound selected from one or more of said structures 1 to 291 .
  • the invention relates to a method of purifying a feedstock comprising a first and a second olefin, which may be identical or which may be different from one another, and by-products, which are selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, or a mixture of two or more thereof, comprising:
  • the by-products in the feedstock are subjected to an anhydride of an organic acid; preferably wherein said anhydrides are the anhydrides of aliphatic, cyclic, alicyclic organic acids having from 1 to 10 carbon atoms, or an aromatic organic acid having from 6 to 10 carbon atoms;
  • the by-products in the feedstock are subjected to an organometallic compound of aluminum; preferably wherein the organometallic compound of aluminum is of formula R 1 R 2 R 3 Al, wherein R 1 , R 2 , and R 3 are independently selected from an aliphatic, cyclic, alicyclic residue having from 1 to 10 carbon atoms, or from aromatic residues having from 6 to 10 carbon atoms.
  • the anhydride of an organic acid is acetic acid; or the organometallic compound of aluminum is trioctyl aluminum.
  • said method consists of step (0).
  • Sixth aspect of the invention Composition comprising a compound that catalyzes metathesis of a first and / or a second olefin and a purified feedstock
  • the invention relates to a composition
  • a composition comprising a compound as defined in any one of the embodiments according to the first aspect or a compound defined in any one of the embodiments according to the second aspect that catalyzes metathesis of a first and/or a second olefin, and a first and/or a second olefin, which are comprised in a feedstock, wherein said feedstock further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, or a mixture of two or more thereof, and wherein said feedstock has been subjected to a purification step as defined in any one of the respective embodiments according to the first aspect.
  • the invention relates to a composition consisting of said compound and said first and/or second ole; or consisting of said compound and a feedstock which contains said first and/or second olefin.
  • Seventh aspect of the invention Method of increasing reactivity of a compound that catalyzes a metathesis reaction
  • the invention relates to a method of increasing the reactivity of a compound as defined in any one of the embodiments according to the first aspect that catalyzes a metathesis reaction of a first and a second olefin such that the molar ratio of said compound to the first or the second olefin is less than 1 : 500, and the conversion of the first or the second olefin is at least 30 %, wherein said first and said second olefin are comprised in a feedstock, wherein said feedstock further comprises at least one by-product selected from the group consisting of water, alcohols, aldehydes, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis basic catalyst poisons, or a mixture of two or more thereof, comprising step (0) and, optionally, subsequent to step (0), the following step (i):
  • the feedstock is subjected to said compound for a period of from 2 to 100 h, preferably 5 to 90 h, more preferred 10 to 80 h, and still more preferred 15 to 70 h.
  • the catalyst is slowly added to the substrate at a rate of from 0.01-10 ppmwt catalyst per hour.
  • said method consists of steps (0) and (i).
  • the invention relates to a method of metathesizing a first olefin and/or a second olefin, comprising at least steps (i) to (iii):
  • the catalyst is slowly added to the first and/or second olefin at a rate of from 0.01-10 ppmwt catalyst per hour, or any other rate as defined in the first aspect of the invention.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of 1 : 7,500 or less, and the corresponding conversion is at least 30 %, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of 1 : 10,000 or less, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of 1 : 20,000 or less, or 1 : 50,000 or less, or 1 : 100,000 or less, or 1 : 500,000 or less, or 1 : 1,000,000 or less, and the corresponding conversion is at least 30%, or at least 40 %, or at least 50 %, or at least 60 %, or at least 70 %, or at least 80 %, or at least 90 %, respectively.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of a lower limit of 1 : 2,000,000, or 1 : 3,000,000 or 1 : 4,000,000, respectively.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of 1 : 500 to 1 : 50,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of 1 : 1,000 to 1 : 40,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of from 1 : 2,500 to 1 : 30,000 or less, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %.
  • the catalyst is added at a rate to enable the metathesis reaction to proceed at a molar ratio of the catalyst to the first and/or the second olefin of 1 : 5,000 to 1 : 30,000 or less, or from 1 : 10,000 to 1 : 30,000, or from 1 : 15,000 to 1 : 30,000, and the corresponding conversion is from 30 to 100 %, or from 50 to 100 %, or 60 to 100 %, respectively.
  • said method consists of steps (i) to (iii).
  • the invention relates to a compound of formula: wherein
  • R 6 is substituted in 2- and 4-position with respect to O.
  • R 6 is substituted in 3- and 4-position.
  • R 6 is substituted in 2-, 3- and 4-position.
  • R 6 is substituted in 2-, 5- and 4-position.
  • R 6 is substituted in 3-, 5- and 4-position.
  • R 6 is substituted 2-, 6- and 4-position.
  • R 6 is substituted in 2-, 3-, 5- and 4-position.
  • R 6 is substituted in 2-, 3-, 6- and 4-position.
  • R 6 is substituted in 2-, 3-, 5-, 6- and 4-position.
  • the substituent of residue R 6 in 4-position may be independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy.
  • residue R 6 may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of: halogen, dialkylamino, cyano, optionally substituted alkyl, optionally substituted alkyloxy, optionally substituted aryl, optionally substituted aryloxy.
  • R 1 is phenyl or alkyl; optionally substituted;
  • R 2 and R 3 can be the same or different and are hydrogen, optionally substituted alkyl;
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted;
  • the substituent of residue R 6 in 4-position may be independently selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the further substituents of residue R 6 , i.e.
  • a substituent in 2- position with respect to O, or in 3-position, or in 2- and 3-position, or in 2- and 5-position, or in 3- and 5-position, or in 2- and 6-position, or in 2-, 3- and 5-position, or in 2-, 3- and 6-position, or in 2-, 3-, 5- and 6-position may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • R 1 is phenyl or alkyl, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy, respectively;
  • R 2 and R 3 can be the same or different and are hydrogen or optionally substituted alkyl;
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and the substituent of residue R 6 in 4-position may be independently selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the further substituents of residue R 6 , i.e.
  • a substituent in 2- position with respect to O, or in 3-position, or in 2- and 3-position, or in 2- and 5-position, or in 3-, and 5-position, or in 2- and 6-position, or in 2-, 3- and 5-position, or in 2-, 3- and 6-position, or in 2-, 3-, 5- and 6-position, may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • R 1 is phenyl or alkyl, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy;
  • R 2 and R 3 can be the same or different and are hydrogen, C(CH 3 ) 3 or C(CH 3 ) 2 C 6 H 5 ;
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted; and the substituent of residue R 6 in 4-position may be independently selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the further substituents of residue R 6 , i.e.
  • a substituent in 2-position with respect to O, or in 3-position, or in 2- and 3-position, or in 2- and 5-position, or in 3- and 5-position, or in 2- and 6-position, or in 2-, 3- and 5-position, or in 2-, 3- and 6-position, or in 2-, 3-, 5- and 6-position may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoroprop-2-yloxy; 2,6-diphenylphenoxy; 9-phenyl-fluorene-9-yloxy; t-
  • a substituent in 2-position with respect to O, or in 3-position, or substituents in 2- and 3-position, or in 2- and 5-position, or in 3- and 5-position, or in 2- and 6-position, or in 2-, 3- and 5-position, or in 2-, 3- and 6-position, or in 2-, 3-, 5- and 6-position, may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • the substituent of R 6 in 4-position may be independently selected from the group consisting of: fluoro, chloro, bromo, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy: phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; and the further substituents of residue R 6 , i.e.
  • a substituent in 2-position with respect to O, or in 3-position, or in 2- and 3-position, or in 2- and 5-position, or in 3- and 5-position, or in 2- and 6-position, or in 2-, 3- and 5-position, or in 2-, 3- and 6-position, or in 2-, 3-, 5- and 6-position may be the same or may be different from the substituent in 4-position and may be independently selected from the group consisting of fluoro, chloro, bromo, dimethylamino, diethylamino, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, methoxy, ethoxy, propyloxy, butyloxy, t-butyloxy, trifluoromethyl, phenyl optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy; phenoxy optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
  • residue R 6 is a phenyl ring which is substituted in 2- and 4-position independently with halogen and in 6-position with phenyl, which optionally may be substituted with halogen, alkyl, alkyloxy, phenyl, optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy, phenoxy, optionally substituted with halogen, alkyl, alkyloxy, phenyl, phenoxy.
  • M Mo or W;
  • R 1 is selected from 2,6-diisopropylphenyl, 2,6-dichlorophenyl;
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3 ;
  • R 3 is H ;
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy;
  • This type of catalyst according to the invention is e.g. represented by compounds 183 and 184.
  • said phenyl ring R 6 may bear - besides the substituents in 2, 6 and 4-position with respect to O - also substituents in 3- and / or 5-position.
  • M Mo or W
  • R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted
  • R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • R 6 is a phenyl ring which is substituted in 2- and 6-position by substituents via carbon atoms, and in 4-position by a substituent via any atom.
  • any atom used herein encompasses halogen, carbon, nitrogen, oxygen.
  • M Mo or W
  • R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted
  • R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • M Mo or W
  • R 1 is phenyl or alkyl, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy
  • R 2 and R 3 can be the same or different and are hydrogen, C(CH 3 ) 3 , or C(CH 3 ) 2 C 6 H 5
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • the substituent of residue R 6 in 4-position may be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the further substituents of residue R 6 , i.e.
  • substituents in 2- and 6-position with respect to O may be the same or may be different from one another, and may be selected from the group consisting of optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy
  • the substituent of residue R 6 in 4-position may be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the further
  • substituents in 2- and 6-position may be the same or may be different from one another, and may be selected from the group consisting of optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • Examples are compounds 3, 4, 5, 7, 14, 15, 17, 18, 19, 70, 33, 34, 35, 36, 37, 41, 42, 43, 44, 63, 64, 65, 66, 67, 68, 69, 120, 121, 122, 125, 126, 127, 130, 131, 132, 133, 134, 135, 140, 141, 142, 146, 149, 150, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 173, 187, 188.
  • said phenyl ring R 6 may bear - besides the substituents in 2-, 6- and 4-position with respect to O - also substituents in 3- and / or 5-position.
  • M Mo or W
  • R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted
  • R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • M Mo or W
  • R 1 is phenyl or alkyl, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy
  • R 2 and R 3 can be the same or different and are hydrogen, C(CH 3 ) 3 , C(CH 3 ) 2 C 6 H 5
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • the substituent of residue R 6 in 4-position may be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the substituents of residue R 6 in 2- and 6-position may be the same or may be
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy
  • the substituent of residue R 6 in 4-position may be selected from the group consisting of: halogen, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy; and the
  • M Mo or W
  • R 1 is aryl, heteroaryl, alkyl, or heteroalkyl; optionally substituted
  • R 2 and R 3 can be the same or different and are hydrogen, alkyl, alkenyl, heteroalkyl, heteroalkenyl, aryl, or heteroaryl; optionally substituted
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy
  • Examples are compounds 11, 13, 16, 32, 60, 123, 136, 145, 189, 261,
  • Such compounds which bear a 4-bromo-(2,3,5,6-tetraphenyl)phenyl moiety may have a positive impact on catalytic activity compared to their debromo analogues, i.e. which are substituted in 4-position with hydrogen. This positive impact may result in a higher conversion in the range of from 10 to 30 %.
  • the invention relates to a compound of formula: wherein
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy
  • Such compounds exhibit good activity in ethenolysis.
  • Compounds are e.g. compounds 178 and 233.
  • the invention relates to a compound of formula wherein
  • [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy, optionally substituted encompasses the substitution of one or both of the naphthyl rings with one or more substituents selected from the group consisting of: halogen, hydroxyl, protected hydroxyl, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is phenyl or alkyl, optionally independently substituted with halogen, C 1-4 dialkylamino, C 1-4 alkyl, C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy
  • R 2 and R 3 can be the same or different and are hydrogen, C(CH 3 ) 3 , or C(CH 3 ) 2 C 6 H 5
  • R 5 is alkyl, alkoxy, heteroalkyl, aryl, aryloxy, heteroaryl, silylalkyl, silyloxy, optionally substituted
  • R 4 is [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy, optionally substituted.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy
  • R 4 is [8-(naphthalene-1-yl)-naphthalene-1-yl]oxy, optionally substituted.
  • Examples are compounds 192, 196, 214, 217, 220.
  • Such compounds may have a positive impact on catalytic activity regarding ethenolysis, cross metathesis and homo metathesis.
  • the invention relates to a compound of formula wherein
  • 8-phenlynaphthalene-1-yl)oxy encompasses the substitution of the phenyl ring or the naphthyl ring or the phenyl and the naphthyl ring with one or more substituents selected from the group consisting of: halogen, hydroxyl, protected hydroxyl, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; (8-phenlynaphthalene-1-yl)oxy, optionally substituted
  • R 4 is (8-phenlynaphthalene-1-yl)oxy, optionally substituted.
  • Examples are compounds 218, 216, 247, 246, 288, 269.
  • the invention relates to a compound of formula: wherein
  • quinoline-8-yl, optionally substituted encompasses the substitution of the ring system with one or more substituents selected from the group consisting of: halogen, hydroxyl, protected hydroxyl, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy
  • the invention relates to a compound of formula: wherein
  • the substituent in 2-position may be selected from the group consisting of: halogen, hydroxyl, protected hydroxyl, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoroprop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-
  • An exemplary compound is compound 152 .
  • the invention relates to a compound of formula: wherein
  • the substituents in 2- and 6-position may be independently selected from the group consisting of: halogen, hydroxyl, protected hydroxyl, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • M Mo or W
  • R 1 is selected from 2,6-dimethylphenyl, 2,6-diisopropylphenyl, 2,6-dichlorophenyl, 2,3,4,5,6-pentafluorophenly, 2-trifluoromethyl, 2,6-di(trifluoromethyl)phenyl, adamant-1-yl
  • R 2 is -C(CH 3 ) 2 C 6 H 5 or -C(CH 3 ) 3
  • R 3 is H
  • R 5 is selected from pyrrol-1-yl; 2,5-dimethyl-pyrrol-1-yl; triphenylsilyloxy; triisopropylsilyloxy; 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy; 2-methyl-1,1,1,3,3,3-hexafluoroprop-2-yloxy; 9-phenyl-fluorene-9-yloxy; 2,6-diphenylphenoxy; t-
  • Exemplary compounds are compounds 73, 74, 84, 85, 89, 6, 8, 62, 175, 176, 177, 178, 179, 185, 195, 199, 202, 203, 204, 205, 232, 233, 270, 271, 272, 273, 274.
  • metathesis refers to alkene (olefin) metathesis.
  • cross metathesis encompasses the reaction between two different olefins.
  • ring opening metathesis encompasses the ring opening of a cyclic olefin.
  • ring opening polymerization metathesis encompasses the ring opening of a cyclic olefin, wherein the ring-opened product polymerizes in a chain-growth polymerization to form a polymer containing olefinic bonds.
  • ring closing metathesis encompasses the ring closing of a diene.
  • ethenolysis encompasses the reaction of an olefin having an internal olefinic bond with ethylene.
  • homo-metathesis encompasses the formation of an internal olefin from two identical olefins.
  • conversion or " conversion degree" is defined as 100 - [final moles of first or second olefin * 100 % / initial moles of first or second olefin].
  • olefinic double bond refers to a carbon-carbon double bond or ethylenic double bond.
  • olefin refers to any species having at least one ethylenic double bond such as normal and branched chain aliphatic olefins, cycloaliphatic olefins, or aryl substituted olefins. Olefins may comprise terminal double bond(s) (" terminal olefin ”) and/or internal double bond(s) (“ internal olefin ”) and can be cyclic or acyclic, linear or branched, optionally substituted.
  • the total number of carbon atoms can be from 1 to 100, or from 1 to 40; the double bonds of a terminal olefin may be mono- or bi-substituted and the double bond of an internal olefin may be bi-, tri-, or tetrasubstituted. In some cases, an internal olefin is bisubstituted.
  • Non-limiting examples of molecules comprising terminal olefins are substituted and unsubstituted linear alkyl internal olefins such as C 4 -C 30 olefins (e.g., 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, allylbenzene, allyltrimethylsilane, methyl-10-undecenoate, allylboronic acid pincol ester, allylbenzylether, N-allyl-4-methylbenzenesulfonamide, allylaniline, methyl-9-decenoate, allyloxy(tert-butyl)dimethyl silane, allylcyclohexane, etc.).
  • linear alkyl internal olefins
  • cyclic olefin refers to any cyclic species comprising at least one ethylenic double bond in a ring.
  • the atoms of the ring may be optionally substituted.
  • the ring may comprise any number of carbon atoms and/or heteroatoms. In some cases, the cyclic olefin may comprise more than one ring.
  • a ring may comprise at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, or more, atoms.
  • Non-limiting examples of cyclic olefins include norbornene, dicyclopentadiene, bicyclo compounds, oxabicyclo compounds, and the like, all optionally substituted.
  • Bicyclo compounds are a class of compounds consisting of two rings only, having two or more atoms in common.
  • Oxabicyclo compounds are a class of compounds consisting of two rings only, having two or more atoms in common, wherein at least one ring comprises an oxygen atom.
  • substituted is contemplated to include all permissible substituents of organic compounds, " permissible " being in the context of the chemical rules of valence known to those of ordinary skill in the art.
  • substituents include, but are not limited to, alkyl, aryl, arylalkyl, cyclic alkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, perhaloalkoxy, arylalkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroarylalkoxy, azido, amino, halogen, alkylthio, oxo, acylalkyl, carboxy esters, carboxyl, -carboxamido, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, arylalkylamino, alkylsulfonyl, -car
  • alkyl encompasses saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkyl substituted alkyl groups.
  • a straight chain or branched chain alkyl has about 30 or fewer carbon atoms in its backbone (e.g., C 1 -C 30 for straight chain, C 3 -C 30 for branched chain), and alternatively, about 20 or fewer.
  • cycloalkyls have from about 3 to about 10 carbon atoms in their ring structure, and alternatively about 5, 6 or 7 carbons in the ring structure.
  • an alkyl group may be a lower alkyl group, wherein a lower alkyl group comprises 10 or fewer carbon atoms in its backbone (e.g., C 1 -C 10 for straight chain lower alkyls).
  • alky encompasses C 1 -C 4 alkyl such as methyl, isopropyl or t-butyl.
  • alkyl also encompasses bridged hydrocarbon residues such as the adamantyl residue, particularly the adamant-1-yl residue. Such residue is e.g. disclosed in compounds 9, 16, 46, 48, 49 as residue R 1 .
  • alkyl also encompasses anellated ring systems such as the fluorene-9-yl residue such as the 9-phenyl-fluorene-9-yl residue.
  • t-Bu denotes a tertiary butyl group.
  • alkoxy refers to the group -O-alkyl, wherein alkyl has the meaning as defined above in connection with the term alkyl.
  • a preferred alkoxy residue is 9-phenylfluorene-9-yloxy as disclosed in compounds 28, 29, 30, 47, 49, 53, 58, 72 as residue R 4 and in compounds 49 and 72 as residues R 4 and R 5 .
  • a further preferred alkoxy residue is triphenylmethyloxy (triphenylmethoxy) as disclosed in compound 23, 25, 27, 45, 52 as residue R 4 .
  • a further preferred alkoxy residue is tri(4-methylphenyl)methyloxy [tri(4-methylphenyl)methoxy] as disclosed in compound 62 as residue R 4 .
  • a further preferred alkoxy residue is 2-phenyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy as disclosed in compound 39 as residue R 4 and in compounds 38, 40 as residue R 4 and residue R 5 .
  • a further preferred alkoxy residue is 2-methyl-1,1,1,3,3,3-hexafluoro-prop-2-yloxy as disclosed in compound 71 as residue R 4 and in compound 72 as residue R 4 and residue R 5 .
  • a further preferred alkoxy residue is t-butyloxy as disclosed in compound 90 as residue R 4 and residue R 5 .
  • a further preferred alkoxy residue is 9-phenyl-9-fluorene-9-yloxy as disclosed in compounds 29, 30, 47, 53, 58 as R 4 and in compound 49 and 81 as R 4 and R 5 .
  • alkenyl refers to olefinic groups as described above.
  • the alkenyl group may be optionally substituted with the substituents defined above.
  • aryl refers to aromatic carbocyclic groups, optionally substituted, having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings in which at least one is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl).
  • At least one ring may have a conjugated ⁇ electron system, while other, adjoining rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, and/or heterocyclyls.
  • the aryl group may be optionally substituted, as described herein.
  • carbocyclic aryl groups refers to aryl groups wherein the ring atoms on the aromatic ring are carbon atoms.
  • Carbocyclic aryl groups include monocyclic carbocyclic aryl groups and polycyclic or fused compounds (e.g., two or more adjacent ring atoms are common to two adjoining rings) such as naphthyl groups.
  • the aryl groups may include monocyclic carbocyclic aryl groups and polycyclic or fused compounds (e.g., two or more adjacent ring atoms are common to two adjoining rings) such as naphthyl group.
  • Non-limiting examples of aryl groups include phenyl, naphthyl, tetrahydronaphthyl, indanyl, indenyl, and the like.
  • a preferred aryl residue is 2,6-diisopropylphenyl as defined in compounds 1, 2, 6, 7, 8, 10, 11, 14, 17, 18, 19, 22, 23, 24, 25, 28, 29, 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, 42, 43, 44, 50, 54, 56, 57, 58, 60 as residue R 1 .
  • a further preferred aryl residue is 2,6-dichlorophenyl as defined in compounds 3, 4, 5, 20, 21, 26, 27, 30, 52, 53, 59, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 as residue R 1 .
  • a further preferred aryl residue is 2,6-dimethylphenyl as defined in compounds 8, 12, 13, 15, 39, 40, 45, 47, 51, 55, 61 as residue R 1 .
  • phenoxy refers to the group C 6 H 5 O -.
  • thiophenoxy refers to the group C 6 H 5 S -
  • This phenoxy or thiophenoxy residue may be substituted with up to five substituents independently selected from alkyl, preferably C 1 -C 4 alkyl such as methyl, isopropyl or t-butyl, alkoxy, preferably C 1 -C 4 alkoxy, phenoxy, phenyl, halogen.
  • alkyl preferably C 1 -C 4 alkyl such as methyl, isopropyl or t-butyl
  • alkoxy preferably C 1 -C 4 alkoxy
  • phenoxy, phenyl, halogen preferably 2,6-diphenylphenoxy as defined in compounds 1, 6, 8, 9 as residue R 4 .
  • a further preferred phenoxy residue is 4-bromo-2,6-diphenylphenoxy as defined in compounds 14, 15, 33, 68 as residue R 4 .
  • a further preferred phenoxy residue is 4-fluoro-2,6-diphenylphenoxy as e.g. disclosed in compounds 34, 36, 63, 67 as residue R 4 .
  • a further preferred phenoxy residue is 4-methyl-2,6-diphenylphenoxy as defined in compounds 41, 42, 65 as residue R 4 .
  • a further preferred phenoxy residue is 2,4,6-triphenylphenoxy as defined in compounds 43, 44, 64, 66 as residue R 4 .
  • a further preferred phenoxy residue is 4-fluoro-2,6-dimesitylphenoxy as defined in compounds 35, 37, 69 as residue R 4 .
  • a further preferred phenoxy residue is 2,6-di-tert.-butylphenoxy as defined in compounds 59, 62 as residue R 4 .
  • a further preferred phenoxy residue is 4-bromo-2,6-di-tert.-butylphenoxy as defined in compounds 3, 17 as residue R 4 .
  • a further preferred phenoxy residue is 4-methoxy-2,6-di-tert.-butylphenoxy as defined in compounds 5, 19 as residue R 4 .
  • a further preferred phenoxy residue is 4-methyl-2,6-di-tert.-butylphenoxy as defined in compound 7 as residue R 4 .
  • a further preferred phenoxy residue is 2,4,6-tri-tert.-butylphenoxy as defined in compounds 4, 18 as residue R 4 .
  • a further preferred phenoxy residue is 2,3,5,6-tetraphenylphenoxy as defined in compounds 10, 12 as residue R 4 .
  • a further preferred phenoxy residue is 4-bromo-2,3,5,6-tetraphenylphenoxy as defined in compounds 11, 13, 16 as residue R 4 .
  • a further preferred phenoxy residue is 2,6-di(4-bromophenyl)-3,5-diphenylphenoxy as defined in compounds 53, 54 as residue R 4 .
  • a further preferred phenoxy residue is 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy as defined in compounds 32, 60 as residue R 4 .
  • a further preferred phenoxy residue is as defined in compound 56 as residue R 4 .
  • TBS denotes a t-butyldimethylsilyl group.
  • a further preferred phenoxy residue is as defined in compound 58 as residue R 4 .
  • Me denotes a methyl group.
  • a further preferred phenoxy residue is 4-dimethylaminophenyl-2,6-diphenylphenoxy as residue R 4 as e.g. defined in structures 159, 160, 161, 162, 167, 168, 169, 170.
  • a further preferred phenoxy residue is 2,6-di(2,4,6-triisopropylphenyl)phenoxy as residue R 4 as e.g. defined in structure 174.
  • residue R 4 is quinolone-8-oxy as residue R 4 as e.g. defined in structure 94 and 97 .
  • a preferred thiophenoxy residue is 2,6-diphenylthiophenoxy, 4-bromo-2,6-diphenylthiophenoxy, 4-fluoro-2,6-diphenylthiophenoxy, 4-methyl-2,6-diphenylthiophenoxy, 2,4,6-triphenylthiophenoxy, 4-fluoro-dimesitylthiophenoxy, 2,6-ditert.-butylthiophenoxy, 4-bromo-2,6-di-tert.-butylthiophenoxy, 4-methoxy-2,6-di-tert.-butylthiophenoxy, 4-methyl-2,6-di-tert.-butylthiophenoxy, 2,4,6-tri-tert.-butylthiophenoxy, 2,3,5,6-tetraphenylthiophenoxy, 4-bromo-2,3,5,6-tetraphenylthiophenoxy, 2,6-di(4-bromophenyl)-3,5
  • heteroaryl refers to aryl groups as described herein in which one or more atoms is a heteroatom (e.g., oxygen, nitrogen, sulfur, and the like), optionally substituted.
  • aryl and heteroaryl groups include, but are not limited to, phenyl, aryloxy, pyrrolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, triazolyl, pyrazolyl, pyridinyl, pyrazinyl, pyridazinyl and pyrimidinyl, and the like.
  • a preferred heteroaryl residue is the pyrrol-1-yl residue as e.g. disclosed in compounds 2, 3, 4, 5, 6, 7, 17, 18, 19, 20, 25, 28, 33, 34, 37, 41, 43, 51, 52, 58, 59, 62, 65, 66, 67, 68, 69, 70 as residue R 5 .
  • a further preferred heteroaryl residue is the 2,5-dimethylpyrrol-1-yl residue as e.g. disclosed in compounds 1, 8, 9, 10, 11, 12, 13, 14, 15, 16, 21, 22, 23, 24, 26, 27, 29, 30, 31, 32, 35, 36, 39, 42, 45, 44, 47, 57, 61, 63, 64 as residue R 5 .
  • heteroalkyl refers to alkyl groups as described herein in which one or more atoms is a heteroatom (e.g., oxygen, nitrogen, sulfur, and the like).
  • heteroalkyl groups include, but are not limited to, alkoxy, poly(ethylene glycol)-, alkylsubstituted amino, tetrahydrofuranyl, piperidinyl, morpholinyl, etc.
  • halogen refers to F, Cl, Br, I.
  • acyl refers to H, alkyl, alkenyl, aryl, heteroalkyl and heteroaryl groups as defined above, which are linked to another atom or to another moiety such as a olefinic double bond via a carbonyl group.
  • triphenylsilyloxy refers to the preferred group (C 6 H 5 ) 3 SiO which is e.g. disclosed in compounds 2, 20, 21, 22, 24, 46, 49, 50 as residue R 4 and in compounds 46, 50 additionally as residue R 5 .
  • triisopropylsilyloxy refers to the preferred group (CH 3 ) 2 CHSiO as e.g. disclosed in compound 137.
  • feedstock encompasses the compounds used as starting material in the reaction according to the invention, i.e. first olefin and/or said second olefin and further products accompanying said olefin(s). said further olefins are termed as " by-products ".
  • the feedstock comprises at least 99 % by weight of the first and/or the second olefin based on the total weight of the feedstock, the remainder being by-products, or at least 99.5 % by weight.
  • By-products are e.g. water, alcohols, aldehydes, peroxides, hydroperoxides.
  • first or second olefin is in one embodiment synonymously used with the term "first and second olefin”.
  • the term " physical purification" encompasses: distilling said by-products off, or distilling said feedstock, or adsorbing said by-products.
  • chemical purification encompasses: subjecting the by-products to a chemical reaction.
  • chemical reaction encompasses a reaction in which at least one compound such as a by-product accompanying said first and/or second olefin is converted into another compound.
  • chemical reaction refers to a process in which in a compound a new bond is formed.
  • substrate encompasses the first and/or the second olefin, i.e. the olefin(s) to be converted in a metathesis reaction.
  • protic material encompasses any material that is suitable to release a proton, or from which protons may be removed.
  • polar material encompasses any material that has polar groups such as hydroxyl groups, carboxylic groups, aldehyde groups, cyano groups, nitrile groups, sulfonate groups, phosphate groups, ester groups.
  • Lewis base catalyst poisons encompasses any compound which has a free pair of electrons.
  • means in connection with purification encompasses any method or material which is/are suitable to at least partially destroy or remove a by-product that is contained in a feedstock comprising a first and a second olefin.
  • optionally substituted encompasses the substitution of a phenyl ring or an alkyl chain with one or more substituents selected from the group consisting of: halogen, hydroxyl, protected hydroxyl, C 1-4 dialkylamino, optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkyloxy, optionally substituted phenyl, optionally substituted phenyloxy.
  • protected hydroxyl encompasses the protection with Si-containing groups such as trimethylsilyl (TMS), triethylsilyl (TES), t-butyldimethylsilyl (TBS, TBDMS), triisopropylsilyl (TIPS), and t-butyldiphenylsilyl (TBDPS).
  • TMS trimethylsilyl
  • TES triethylsilyl
  • TBDMS t-butyldimethylsilyl
  • TIPS triisopropylsilyl
  • TDPS t-butyldiphenylsilyl
  • Example 1 N-[(2,5-dimethyl-1H-pyrrol-1-yl)(2-methyl-2-phenylpropylidene)2,4,6-triphenylphenoxymolybdenumylidene]-2,6-bis(propan-2-yl)aniline (novel compound 44 )
  • Metathesis catalysts were tested in RCM of diethyl diallylmalonate. The reaction was characterized by the conversion data. Compounds 1, 10 and 154 are known compounds, compounds 11, 42, 123, 142, 162, 168, 178 are novel. Results are summarized at Table 2. Table 2. Results of diethyl diallylmalonate ( 1 ) self-metathesis in the presence of different metathesis catalysts at 760 Torr Entry Cat. No. Molar ratio Catalyst/ olefin T (°C) Time [h] Solvent c (mol/L) Conv.
  • Diethyldiallylmalonate was purchased from Sigma-Aldrich. It was purged with nitrogen and transferred to the glovebox. It was percolated twice on 2 ⁇ 25 weight% activated alumina, and stored on molecular sieve.
  • the substrate was further stirred with 0.037-0.1 mol% triethylaluminium (r.t. during 1 h) to deactivate free phenol and water traces.
  • Metathesis catalysts were tested in HCM of 2-allylphenylacetate using different substrate/catalyst ratios. The reaction was characterized by the conversion data. Catalysts according to the invention were compared to known compounds 1 and 10 . Prior to the metathesis reaction, novel compound 2 was purified by means of Et 3 Al.
  • Allylbenzene was purchased from Sigma-Aldrich (A29402-100ML, Lot No.: 55496LMV, Certificate of analysis: 99.9%). In house GCMS analysis: 99.64% allylbenzene, 0.27% cinnamaldehyde, 0.07 % unknown impurities. Hydroperoxide content: 0.68 mol% by titration. Water content by KF titration: 973 ppm, 0.63 mol%.
  • Crude allylbenzene was pretreated with different amount of Oc 3 Al. After pretreatment the crude substrate was applied in metathesis reaction. The reaction was characterized by the conversion data and the necessary amount of Oc 3 Al could be optimized.
  • Table 7 presents the application of Oc 3 Al pretreatment in allylbenzene self-metathesis in the presence of 50 mol ppm of known catalyst 1 and novel catalysts 178, 162, 168, 183, 184 and 123: Table 7.
  • Application of Oc 3 Al pretreatment in allylbenzene ( 1 ) self-metathesis in the presence of 50 mol ppm catalysts Entry Oc 3 Al [mol%] Conversion [%] a 1 178 162 168 183 184 11 123 1 0,9 91 18 48 64 48 85 34 90 2 1 95 83 91 92 58 94 88 92 3 1,10 85 91 90 92 85 93 91 91 4 1,20 12 90 11 87 77 87 82 93
  • Pretreatment conditions: 18 h stirring at r.t, Catalyst / substrate 1 : 20 000, Metathesis conditions: 4h, r.t.
  • Table 8 presents the effect of the pretreatment time. It was found that under the given conditions the reaction goes to completion practically in 2-4 h. Table 8. Study of the effect of pretreatment time of crude allylbenzene in self-metathesis catalyzed by known catalyst 1 Purification time [h] Conv.
  • Trioctylaluminum which allows a safe handling, efficiently destroys impurities in allylbenzene substrate and allows to reach high conversion even at such a low catalyst loading as of 50 mol ppm.
  • Crude diethyl diallylmalonate was purchased from Sigma-Aldrich, its water content by Karl-Fischer titration was 346 weight ppm (0.46 mol%).
  • the solution of the crude substrate was pretreated (stirred) with Oc 3 Al then applied in RCM reaction using novel compound 11 as catalyst under standard conditions.
  • Table 10 shows the results of the improved conversion if purification period is prolonged: Table 10.
  • the experiment was repeated with the difference that the pretreatment time was extended to 60 h, and that the catalyst was added in four portions of 8.25 mole %, respectively. After a period of 2 h subsequent to the addition of the first portion, the conversion was 38 %. Then the second portion was added. After further 2 h, the conversion was 84 %. Then the third portion was added. After further 2 h, the conversion was 93 %. Then the last portion was added. After further 2 h, the conversion was 94 %.
  • Performance of catalysts was compared in ethenolysis of purified unsaturated triglycerides.
  • the purification method was a chemical pretreatment with trialkylaluminum.
  • Triglyceride was subjected to ethylene at a temperature of 50 °C and a pressure of 10 bar for 18 hours using various amounts of catalyst.
  • Metathesis reaction was characterized by the conversion data.
  • the catalysts were used in the same amount [1000 ppm (weight) - 250 ppm (weight) - 25 ppm (weight) respectively], their molar ratio is depending on their molecular weight. Normalized conversion was obtained by linear extrapolation of real conversion calculated from real molar quantity.
  • Table 11 shows the superior results of novel catalysts 123 and 124 in which R 6 is phenyl substituted with phenyl in 2-,3-,5- and 6-position, and 4-position is substituted with bromine compared to known catalyst 154 , which bears hydrogen in 4-position of the phenyl moiety.
  • Table 11 Compound 154 123 124 C 1000 ppm (weight) catalyst [%] 61 84 79 C norm 1000 ppm (weight) catalyst [%] 63 94 102 C 250 ppm (weight) catalyst [%] 39 49 C norm 250 ppm (weight) catalyst [%] 44 63
  • Table 12 shows the results of catalysts in which R 6 is a phenyl ring which is substituted in 2-, 4- and 6-position, wherein the 2- and 6-position are substituted by substituents via a carbon atom, and the substituent in 4-position may be attached to the phenyl ring via any atom.
  • Compound 113 is known, the other compounds are novel.
  • Table 13 shows the results of further catalysts in which R 6 is a phenyl ring which is substituted in 2-, 4- and 6-position, wherein the 2- and 6-position are substituted by substituents via a carbon atom, and the substituent in 4-position is fluorine.
  • Compounds 35 , 122 , 127 , 131 and 135 are novel Table 13 Compound 127 122 35 135 131 C 1000 ppm (weight) catalyst [%] 87 87 77 76 93 C norm 1000 ppm (weight) catalyst [%] 81 78 74 80 90
  • Table 14 shows the results of novel catalysts 178 and 233 in which R 6 is a phenyl ring which is substituted in 2- and 6-position via a phenyl moiety.
  • Table 14 Compound 178 233 C 1000 ppm (weight) catalyst [%] 82 87 C norm 1000 ppm (weight) catalyst [%] 70 87 C 250 ppm (weight) catalyst [%] 46 C norm 250 ppm (weight) catalyst [%] 39
  • Table 15 shows the efficacy of the novel compounds 192, 196, 214, 216, 217, 220, 246, 247, 269, 288 in the homo cross metathesis of methyldecenoate (HCM of DAME), in the homo cross metathesis of allylbenzene (HCM of AB), in the ring closing metathesis of diethyl diallylmalonate (RCM of DEDAM) and in ethenolysis of unsaturated glycerides.
  • HCM of DAME methyldecenoate
  • HCM of AB homo cross metathesis of allylbenzene
  • RCM of DEDAM diethyl diallylmalonate
  • Table 16 shows the efficacy of novel catalysts 207, 208, 214, 216, 220 in HCM of allylbenzene. Allylbenzene was physicochemically treated before metathesis reaction, which means that it was percolated on an activated basic alumina layer (20 weight %). Then it was allowed to stand on 20 % molecular sieve at least 1 day before metathesis reaction. Table 16 Compound 207 214 208 220 216 C 50 ppm (mole catalyst loading [%] 82 81 83 68 72
  • HCM reactions were carried out in a glovebox atmosphere at r.t. for 4h in a vented vial.
  • EtOAc samples were filtered through on a silica layer and analysed by GCMS-FID. The used catalysts are all novel.
  • the substrate was purified by a physical treatment method, i.e. percolation on activated alumina layer.
  • the reaction was characterized by the conversion data. Data are summarized in Table 18.
  • Table 18 Compound 10 11 32 154 123 124 C 50 ppm (mole catalyst loading) [%] not tested 94 75 60 90 80 C 33 ppm (mole catalyst loading) [%] 79 80 77 not tested 68 67
  • Compounds 10 , 11 and 32 are Mo-complexes, whereas compounds 154 , 123 and 124 are W-complexes. Compounds 10 and 154 are known, compounds 11 , 32 , 123 and 124 are novel.
  • Compound 10 has a 2,3,5,6-tetraphenlyphenoxy compound as ligand R 4 , whereas compound 11 is the respective 4-bromo-2,3,5,6-tetraphenylphenoxy compound and compound 32 is the 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy analogue.
  • R 1 in each case is 2,6-diisopropylphenyl.
  • Compound 154 bears a 2,3,5,6-tetraphenylphenoxy residue as ligand R 4 , whereas compound 123 is the respective 4-bromo-2,3,5,6-tetraphenylphenoxy compound and compound 124 the 4-bromo-2,6-di(4-bromophenyl)-3,5-diphenylphenoxy analogue.
  • R 1 in each case is 2,6-dichlorophenyl.
  • the new catalysts exhibit excellent activity.

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Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8362311B2 (en) 2009-09-30 2013-01-29 Massachusetts Institute Of Technology Highly Z-selective olefins metathesis
EP2969204A2 (de) 2013-03-14 2016-01-20 XiMo AG Molybdän- oder wolframkomplexe als olefinmetathesekatalysatoren und reaktionen unter verwendung dieser katalysatoren
US20140330018A1 (en) * 2013-05-01 2014-11-06 Massachusetts Institute Of Technology Metathesis catalysts and methods thereof
US10071950B2 (en) 2013-07-12 2018-09-11 Ximo Ag Use of immobilized molybdenum- and tungsten-containing catalysts in olefin cross metathesis
US10427146B2 (en) 2013-10-01 2019-10-01 Ximo Ag Immobilized metathesis tungsten oxo alkylidene catalysts and use thereof in olefin metathesis
EP3215516B1 (de) * 2014-11-05 2020-01-08 Massachusetts Institute Of Technology Metathesekatalysatoren und verfahren dafür
JP6696435B2 (ja) * 2014-12-26 2020-05-20 Ａｇｃ株式会社 オレフィンの製造方法
JP6583289B2 (ja) * 2014-12-26 2019-10-02 Ａｇｃ株式会社 含塩素含フッ素オレフィンの製造方法
US10351664B2 (en) * 2015-03-09 2019-07-16 Zeon Corporation Resin molded body, resin film, and injection molded article
US10519288B2 (en) * 2015-03-09 2019-12-31 Zeon Corporation Resin molded body manufacturing method, resin film manufacturing method, and injection molded article manufacturing method
CN108697072A (zh) 2015-11-18 2018-10-23 普罗维维股份有限公司 用于产生昆虫信息素及相关化合物的微生物
US9776179B2 (en) 2015-11-18 2017-10-03 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US10744494B2 (en) 2015-12-23 2020-08-18 Ximo Ag Immobilized metal alkylidene catalysts and use thereof in olefin metathesis
GB201604110D0 (en) * 2016-03-10 2016-04-20 Givaudan Sa Preparation of macrocyclic lactones
EP3464311A4 (de) 2016-06-06 2020-03-18 Provivi, Inc. Halb-biosynthetische herstellung von fettalkoholen und fettaldehyden
US11020730B2 (en) 2016-07-15 2021-06-01 Massachusetts Institute Of Technology Halogen-containing metathesis catalysts and methods thereof
JP7153937B2 (ja) 2017-02-17 2022-10-17 プロビビ インコーポレイテッド オレフィンメタセシスによるフェロモンおよび関連材料の合成方法
WO2018213554A1 (en) 2017-05-17 2018-11-22 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
US11332426B2 (en) 2017-09-22 2022-05-17 Trustees Of Boston College Method of preparing trisubstituted ethylene compounds
EP3768691A1 (de) 2018-03-22 2021-01-27 Verbio Vereinigte BioEnergie AG Tetraphenylphenoxy-wolfram-oxyalkyliden-komplexe, verfahren zu ihrer herstellung und ihre verwendung
US20220227797A1 (en) * 2019-05-27 2022-07-21 Verbio Vereinigte Bioenergie Ag Tungsten imido alkylidene o-bitet and o-binol complexes and use thereof in olefin metathesis reactions
US10995049B2 (en) 2019-07-19 2021-05-04 California Institute Of Technology Total synthesis of prostaglandin J natural products and their intermediates
WO2021188337A1 (en) 2020-03-19 2021-09-23 Exxonmobil Chemical Patents Inc. Pentavalent dimeric group 6 transition metal complexes and methods for use thereof
US20230203072A1 (en) * 2020-05-27 2023-06-29 Verbio Vereinigte Bioenergie Ag Air-stable imido alkylidene complexes and use thereof in olefin metathesis reactions
CN113980097B (zh) * 2021-12-29 2022-03-29 浙江湃肽生物有限公司南京分公司 棕榈酰三肽-5的纯化方法
CN114230702B (zh) * 2022-01-17 2023-10-13 万华化学集团股份有限公司 一种萘氧基骨架的烯烃聚合催化剂、制备方法与应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6121473A (en) 1998-02-19 2000-09-19 Massachusetts Institute Of Technology Asymmetric ring-closing metathesis reactions
US20080119678A1 (en) 2006-11-22 2008-05-22 Massachusetts Institute Of Technology Olefin metathesis catalysts and related methods
US20110007742A1 (en) 2005-07-01 2011-01-13 Cisco Technology, Inc. Facilitating Mobility for a Mobile Station
US20110015430A1 (en) 2009-07-15 2011-01-20 Massachusetts Institute Of Technology Catalysts and processes for the formation of terminal olefins by ethenolysis
US20110077421A1 (en) 2009-09-30 2011-03-31 Massachusetts Institute Of Technology Highly z-selective olefins metathesis

Family Cites Families (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1037866A (en) * 1962-05-28 1966-08-03 Ethyl Corp Improved process for preparing alpha olefins of high vinyl olefin content
BE755794A (fr) * 1969-09-08 1971-03-08 Polymer Corp Procede de purification d'hydrocarbures olefiniques
US3689584A (en) * 1970-08-24 1972-09-05 Ethyl Corp A chemical process of separating olefins from aluminum alkyls by forming complexes of the aluminum alkyls which are insoluble in the olefins
US3696161A (en) * 1970-09-30 1972-10-03 Ethyl Corp A chemical process of separating hydrocarbyl aluminum from olefins by the use of 2:1 complexes of aluminum alkyls and an alkali metal salt
DE2845974A1 (de) * 1978-10-21 1980-04-30 Basf Ag Verfahren zur herstellung von carbonsaeureestern vicinaler glykole
IN160358B (de) 1983-01-10 1987-07-11 Thiokol Corp
US4637197A (en) * 1984-10-15 1987-01-20 Epoxy Technology, Inc. Method and compositions for removal of moisture
JPH0428714A (ja) 1990-05-23 1992-01-31 Nippon Zeon Co Ltd 高重合活性ジシクロペンタジエンの製造法およびその重合法
US5210365A (en) 1990-08-27 1993-05-11 Shell Oil Company Olefin disproportionation catalyst and process
US5194534A (en) * 1991-09-24 1993-03-16 Hercules Incorporated Tungsten-imido catalysts for ring-opening metathesis polymerization of cycloolefins
EP0864595B1 (de) * 1997-03-13 2001-08-16 Borealis Technology Oy Trägerkatalysatoren für die ringöffnende Metathesepolymerisation von Cycloolefinen
DE19744102A1 (de) * 1997-10-06 1999-04-15 Targor Gmbh Katalysatorsystem
WO2001046096A1 (en) 1999-12-21 2001-06-28 Sasol Technology (Pty) Ltd Metathesis process for converting short chain olefins to longer chain olefins
US6720468B2 (en) * 2000-06-30 2004-04-13 Chevron Phillips Chemical Company Lp Process for the removal of conjugated olefins from a monoolefin stream
US7411108B2 (en) * 2000-06-30 2008-08-12 Chevron Phillips Chemical Company Lp Process for the removal of conjugated olefins from a monoolefin stream
US20050124839A1 (en) 2001-06-13 2005-06-09 Gartside Robert J. Catalyst and process for the metathesis of ethylene and butene to produce propylene
CN102936536B (zh) 2002-04-29 2014-01-29 陶氏环球技术有限责任公司 关于种子油工业应用的综合化学方法
US7605217B2 (en) * 2003-11-14 2009-10-20 Exxonmobil Chemical Patents Inc. High strength propylene-based elastomers and uses thereof
CN101821218A (zh) 2007-08-09 2010-09-01 埃莱文斯可更新科学公司 用于处理复分解原料的热方法
EP2183205A4 (de) * 2007-08-09 2013-10-02 Elevance Renewable Sciences Chemische verfahren zur behandlung eines metathese-einsatzmaterials
US9284515B2 (en) 2007-08-09 2016-03-15 Elevance Renewable Sciences, Inc. Thermal methods for treating a metathesis feedstock
BRPI0906685A2 (pt) 2008-01-25 2016-10-11 Massachusetts Inst Technology catalisadores para reações de metátese incluindo metátese de olefina enantiosseletiva, e métodos relacionados
JP5483940B2 (ja) 2009-07-13 2014-05-07 ユニ・チャーム株式会社 吸収体及び吸収性物品
RU2565057C2 (ru) 2009-10-12 2015-10-20 Елевансе Реневабле Сайенсез, Инк. Способы очистки и производства топлива из натурального масляного исходного сырья
US8735640B2 (en) 2009-10-12 2014-05-27 Elevance Renewable Sciences, Inc. Methods of refining and producing fuel and specialty chemicals from natural oil feedstocks
US9051519B2 (en) * 2009-10-12 2015-06-09 Elevance Renewable Sciences, Inc. Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters
US9222056B2 (en) 2009-10-12 2015-12-29 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
JP5557536B2 (ja) 2010-01-26 2014-07-23 シンポ株式会社 油脂回収フィルター
US8598400B2 (en) * 2010-02-08 2013-12-03 Massachusetts Institute Of Technology Efficient methods for Z- or cis-selective cross-metathesis
US8704029B2 (en) 2010-03-30 2014-04-22 Uop Llc Conversion of butylene to propylene under olefin metathesis conditions
EP2556078B1 (de) 2010-04-03 2014-09-24 Studiengesellschaft Kohle MbH Katalysatoren für die alkinmetathese
US8722950B2 (en) 2010-04-26 2014-05-13 Saudi Basic Industries Corporation Process for producing propylene and aromatics from butenes by metathesis and aromatization
US8935891B2 (en) 2011-06-09 2015-01-20 Uop Llc Olefin metathesis catalyst containing tungsten fluorine bonds
DE102011012629A1 (de) 2011-02-28 2012-08-30 Studiengesellschaft Kohle Mbh Metallkomplexe des Molybdäns und Wolframs und ihre Verwendung als Präkatalysatoren für die Olefinmetathese
JP2013014562A (ja) 2011-07-06 2013-01-24 Nippon Zeon Co Ltd タングステン錯体、メタセシス反応用触媒および環状オレフィン開環重合体の製造方法
WO2013192384A1 (en) 2012-06-20 2013-12-27 Elevance Renewable Sciences, Inc. Natural oil metathesis compositions
EP2690838A1 (de) 2012-07-23 2014-01-29 Alcatel Lucent Authentifizierungssystem zur Aufrechterhaltung der Vertraulichkeit geheimer Daten
EP2703081B1 (de) * 2012-09-04 2019-08-07 XiMo AG Molybdän- und wolframkomplexe als olefinmetathese-katalysatoren und reaktionen mit den katalysatoren
KR102202927B1 (ko) 2013-03-14 2021-01-14 윌마르 트레이딩 피티이 엘티디 처리된 복분해 기질 물질 및 이의 제조 및 사용 방법
EP2969204A2 (de) 2013-03-14 2016-01-20 XiMo AG Molybdän- oder wolframkomplexe als olefinmetathesekatalysatoren und reaktionen unter verwendung dieser katalysatoren
MY172162A (en) 2013-03-14 2019-11-15 Wilmar Trading Pte Ltd Methods for treating a metathesis feedstock with metal alkoxides
US10071950B2 (en) 2013-07-12 2018-09-11 Ximo Ag Use of immobilized molybdenum- and tungsten-containing catalysts in olefin cross metathesis
EP3019511B1 (de) 2013-07-12 2019-01-02 XiMo AG Immobilisierte metathesewolframkatalysatoren und verwendung davon bei der olefin-metathese
US10427146B2 (en) 2013-10-01 2019-10-01 Ximo Ag Immobilized metathesis tungsten oxo alkylidene catalysts and use thereof in olefin metathesis
US10858573B2 (en) 2014-01-16 2020-12-08 Wilmar Trading Pte Ltd Olefinic ester compositions and their use as cleaning agents
EP3119738B1 (de) 2014-03-19 2019-01-30 Elevance Renewable Sciences, Inc. Systeme und verfahren zur raffination von erdölrohstoffen und derivaten davon
GB201406591D0 (en) 2014-04-11 2014-05-28 Ximo Ag Compounds
DE102014105885A1 (de) 2014-04-25 2015-10-29 Universität Stuttgart N-Heterozyklische Carbenkomplexe von Metallimidoalkylidenen und Metalloxoalkylidenen und deren Verwendung
WO2016095061A1 (en) 2014-12-17 2016-06-23 Eth Zurich Activation of supported olefin metathesis catalysts by organic reductants
US20170011038A1 (en) 2015-07-06 2017-01-12 David Revelle System and method for multiple factor sorting and user interface thereof
US9776179B2 (en) 2015-11-18 2017-10-03 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
DE102016122096A1 (de) 2016-11-17 2018-05-17 Universität Stuttgart Latente Katalysatoren zur vernetzenden Polymerisation von Dicyclopentadien (DCPD)
DE102017101431A1 (de) 2017-01-25 2018-07-26 Universität Stuttgart Molybdän- und Wolfram-Alkylidin-N-heterozyklische Carben-Komplexe
JP7153937B2 (ja) 2017-02-17 2022-10-17 プロビビ インコーポレイテッド オレフィンメタセシスによるフェロモンおよび関連材料の合成方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6121473A (en) 1998-02-19 2000-09-19 Massachusetts Institute Of Technology Asymmetric ring-closing metathesis reactions
US20110007742A1 (en) 2005-07-01 2011-01-13 Cisco Technology, Inc. Facilitating Mobility for a Mobile Station
US20080119678A1 (en) 2006-11-22 2008-05-22 Massachusetts Institute Of Technology Olefin metathesis catalysts and related methods
US20110015430A1 (en) 2009-07-15 2011-01-20 Massachusetts Institute Of Technology Catalysts and processes for the formation of terminal olefins by ethenolysis
US20110077421A1 (en) 2009-09-30 2011-03-31 Massachusetts Institute Of Technology Highly z-selective olefins metathesis
WO2011040963A1 (en) 2009-09-30 2011-04-07 Massachusetts Institute Of Technology Highly z-selective olefin metathesis

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